You can instruct Rebex components (including Rebex Smtp) to use a custom socket factory which will directly say which IP address Rebex SMTP will use - just follow the steps from this answer.
Apart from the original question, the code for Rebex Smtp would look like this:
using Rebex.Net;
using System.Net;
...
Smtp smtp = new Smtp();
smtp.SetSocketFactory(SimpleSocket.GetFactory(IPAddress.Parse("127.0.0.1")));
smtp.Connect(hostname);
Please note, that you have to assign one of the IP addresses which are configured at the local machine' s network interface.